Fluid Phase Equilibria, 91(1993) 349-386 349

Elsevier Science Publishers B.V., Amsterdam

SEPARATION OF CONSTITUENTS OF FISH OIL USING

SUPERCRITICAL FLUIDS: A REVIEW OF EXPERIMENTAL
SOLUBILITY, EXTRACTION, AND CHROMATOGRAPHIC
DATA

Arne Staby and Jorgen Mollerup

Department of Chemical Engineering, DTH, Building 229, 2800 Lyngby (Denmark)

Key words: experiments, data, critical properties, solubility of gas in liquid, VLE
high pressure, carbon dioxide, cholesterol, fatty acid ester, fatty acid, review, Q-
tocopherol, triglyceride.
(Received May 28, 1993; accepted in final form June 18, 1993)

AESTRACT

The use of supercritical fluids, especially carbon dioxide, in separation of fish

oil and derived compounds has increased the last decade due to the expected
advantages of supercritical separation processes. In pursuit of the design of
supercritical fluid separation processes, phase equilibria and pilot plant data are
essential. In this paper we present a survey of literature references of ex-
perimental phase equilibria and solubility data on binary and multicomponent
systems of supercritical fluids and fish oil or derived compounds, as well as
experimental data on supercritical fluid extraction (WE) and supercritical fluid
chromatography (SFC). The fish oil related compounds include triglycerides, free
fatty acids, fatty acid methyl and ethyl esters, cholesterol, ol-tocopherol,
phospholipids, squalene etc. The list of references include the experimental
pressure and temperature ranges, the number of data points/experiments, and
some remarks to the kind of measurements performed and components involved.
The literature retrieval includes references to the end of 1992 and a few from
1993.

0378-3812/93/$06.00 01993 Elsevier Science Publishers B.V. All rights reserved

350 A. Staby and J. Mollerup I Fluid Phase Equilibna 91 (1993) 349386

INTRODUCTION

In the past two decades there has been a considerable publicity about the
beneficial health effects and nutritional value of fish and fish oils. These reports
often describe the large content of 03 fatty acids in fish oil as the main cause to
such effects. The 03 fatty acids, especially the polyunsaturated eicosapentaenoic
acid (EPA) and docosahexaenoic acid (DHA) have been suggested to have
advantageous effects in the treatment or prevention of diseases affecting human
health, such as coronary heart diseases (Hirai et al., 1987), atherosclerosis
(Connor and Connor, 1990), rheumatoid arthritis (Kremer at al., 1990), cancer
(Reddy et al., 1991), and diabetes (Popp-Snijders et al., 1986). Other commercial
and academic interesting constituents of fish oil are for instance vitamins,
antioxidants, and other trace elements.
The crude fish oils consist primarily of triglycerides containing fatty acids of
different chain-lengths and degree of unsaturation. The content of essential fatty
acids of fish are about 20-42% of the total fat content (Gruger et al., 1964). In
order to make products which have a higher concentration of the essential fatty
acids one can fractionate the raw triglycerides or make a lipase-catalyzed
interesterification of the triglycerides prior to fractionation. To produce the pure
fatty acids or products having very high concentrations of the essential fatty acids,
the triglycerides must be saponified to produce the free fatty acids or their
monoesters. The down stream processing may be performed by conventional
methods or supercritical fluid techniques. The conventional methods for
fractionation and isolation of these components include vacuum distillation, urea
crystallization, hexane extraction, or conventional crystallization having the
disadvantages of requiring high temperature processing resulting in degradation
or decomposition of the thermally labile compounds or employing flammable or
toxic solvents having adverse health effects, respectively. These factors have urged
investigators to study the application of supercritical fluid techniques, such as
supercritical fluid extraction, lipase-catalyzed interesterification of the triglycer-
ides in supercritical fluids, urea fractionation in supercritical fluids and supercri-
tical fluid chromatography as down stream processes to produce the desired
products. At present the supercritical fluid techniques are more expensive than
the conventional methods but developed properly we believe them to be
compatible or even superior to the conventional methods.
In this work two literature surveys are given, the first presents experimentally
measured solubilities and phase equilibria of binary and multicomponent systems
of supercritical fluids and fish oil related compounds, and the second presents
separations of fish oil related compounds using supercritical fluid extraction,
fractionation, and/or chromatography. Other, less exhaustive reviews on SFE of
fish oil related compounds are published in symposium proceedings (Krukonis,
1988, Rizvi et al., 1988, and Greibrokk, 1991). Some relevant papers may not be
A. Staby and J. MolleruplFluid Phase Equilibria 91 (1993) 349-386 351

included, especially original papers written in Japanese, Chinese, or Russian and

Japanese review papers (Saito, 1985, Saito, 1986), Saito, 1986b, Saito, 1986,
Wakabayashi, 1986, Yamaguchi and Murakami, 1986, Suzuki, 1988, Ikawa et al.,
1990, Kobayashi and Kamihira, 1990, Matsuki, 1991, and Nagahama and Suzuki,
1992). We are interested in receiving information about references missing as well
as copies of papers unavailable to us.

DATA OF EXPERIMENTAL MEASUREMENTS

The majority of experimental research of supercritical technology and its

application to fish oil related compounds, such as glycerides, free fatty acids,
methyl and ethyl esters, cholesterol, cc-tocopherol, and squalene can be divided
into two categories. The first category involves the measurements of fundamental
data like solubilities and phase equilibria of the compounds in supercritical fluid
media, and the second involves separation of the compounds using SFE, SFC
and/or super-critical fluid fractionation.

Solubilities and phase equilibria

The experimental methods available for measurement of solubilities and

phase equilibria are described in detail elsewhere (Fornari et al., 1990, Bartle et
al., 1991, and Staby, 1993) and will not be presented here, neither do we intend
to evaluate or correlate the data.
The variety and quantity of experimental measurements of solubilities and
phase equilibria of fish oil related compounds in supercritical fluids are extensive
and so are the number of species. Chrastil (1982) has published a major work of
data on the solubilities of triglycerides and pure fatty acids. He reported
solubilities of tributyrin, tripalmitin, tristearin, triolein, trilinolein, stearic acid,
oleic acid, and behenic acid in supercritical CO,. The measurements were
performed in the temperature range of 313-353 K at pressures of 8-25 MPa.
Inomata et al. (1989b)) have measured phase equilibria of binary systems of
carbon dioxide and fatty acid methyl esters at 4 temperatures in the range of
313.15-343.15 K at pressures of 1.01-20.42 MPa. The esters were methyl myristate,
methyl palmitate, methyl stearate, and methyl oleate. Recently Liong et al. (1992)
presented experimental data of solubilities of fatty acid ethyl esters in CO,. The
solutes were the ethyl esters of oleic acid, eicosatrienoic acid, arachidonic acid,
and DHA and the measurements were performed in the temperature range of
313-373 K at the pressures of 9.0-25.0 MPa. Finally, Staby et al. (1993)) have
published measurements of partition coefficients (K-values) of a mixture of fatty
acid ethyl esters derived from sand launce oil in supercritical fluid carbon dioxide.
The measurements were performed at 283.2, 313.2 and 343.2 K in the pressure
352 A. Staby and J. MolleruplFluid Phase Equilibria 91(1993) 349-386

range of 2.0-21.5 MPa.

The measurement of solubilities of some components present in trace
amounts in fish oil has also gained considerable attention, especially the
solubilities of cholesterol and a-tocopherol in supercritical carbon dioxide have
been determined by several researchers. Thus, Wong and Johnston (1986) have
measured the solubilities of cholesterol in carbon dioxide in the temperature
range of 308.2-333.2 K at the pressures of 10.1-27.9 MPa, while Ohgaki et al.
(1987) have published experimental solubility data of a-tocopherol in carbon
dioxide at the temperatures of 298.2 and 313.2 K in the pressure range of lO.O-
18.3 MPa.
In Figure 1 a typical plot of the solubility of a fish oil ester mixture in carbon
dioxide as a function of the pure carbon dioxide density is presented. The curves
display a similar trend as other natural products like soybean oil (Quirin, 1982)
with the enhanced ester solubility above the critical density (470 kg/m3) of carbon
dioxide. Figure 2 shows the phase diagram of the same system with the
engrossing trend of the curves from 343.2 to 283.2 K. At 343.2 K the phase curve
seems as it would for a binary system with miscibility in both phases, while at
283.2 K the immiscibility in the liquid phase has come into existence, and in
between at 313.2 K appears the trend of an incipient immiscibility.

20-

cu15
3
a lo-

h
5 0.1
1

s
z 0.0
O 200 400 800 800 1000
cn 01 I I I
Go:( Ms
Density of CO2 (kg/rn3) 0 00 100
PeI&Id)

Figure 1. Solubility isotherms of a Figure 2. Pressure-composition dia-

fish oil fatty acid ethyl ester mixture gram for a carbon dioxide + fish oil
in carbon dioxide as a function of fatty acid ethyl ester system, (Staby,
pure CO, density, (Staby, 1993). 1993).
A. Staby and J. MolleruplFluid Phase Equilibria 91 (1993) 349-386 353

The experimental techniques and methods employed performing SFE/super-

critical fluid fractionation or SFC are described in detail in several books
(Schneider et al., 1980, McHugh and Krukonis, 1986, Stahl et al., 1987, and
Smith, 1988) and will not be presented here, neither do we intend to evaluate or
compare the data.
An abundance of work on the separation of fish oil related compounds using
SFE and/or supercritical fluid have been done since Passino (1949) described the
solexol process for fractionation of fish oils using subcritical propane. Zosel
(1978) has described the use of supercritical ethane to extract and fractionate
triglycerides from fish liver oil with a recirculation apparatus. He found that the
molecular mass and the iodine value, an expression of the degree of unsaturation
of the triglycerides, rose during the extraction and fractionation process.
Eisenbach (1984) utilized the same experimental procedure to separate EPA
ethyl ester from a mixture of fatty acid ethyl esters derived from codfish oil by
means of supercritical carbon dioxide. Like Zosel (1978), he found that the low
molecular weight components were extracted preferentially, causing the high
molecular weight components (like EPA ethyl ester) to be collected in some of
the final fractions. After a two-step process of some of the fractions he achieved
a yield of 79.8% of the initial EPA content with a purity of 91.9%. The impurities
were mainly eicosenoic acid ethyl ester. Arai and Saito (1986) have described the
fractionation of a model mixture of fatty acids and fatty acid methyl esters from
sardine oil by extractive urea crystallization using supercritical CO, as the solvent.
This method employs both the ability of a supercritical fluid to separate the fatty
acids by chain length as well as the ability of urea crystallization to separate the
fatty acids by their degree of unsaturation.
Lately, the interest in the extraction of components present in trace amounts
in fish oil, such as vitamins or contaminations, has arisen. Thus, Yamaguchi et al.
(1986) have performed a series of SFEs of carotenoids from freeze-dried krill oil
using carbon dioxide as the solvent in the temperature range of 313-353 K at a
pressure of 25 MPa. The Ph. D.-thesis of Elvevoll (1988) demonstrates some of
the variety of trace components that might be extracted from fish oil using
supercritical carbon dioxide. She accomplished to extract components like
ubiquinone, cholesterol, a-tocopherol, retinol, squalene, and cholecalciferol from
codfish viscera oil at temperatures between 309 and 328 K in the pressure range
of 8-28 MPa. Recently, Krukonis (1989) and Nam et al. (1989, 1990, 1991) have
among others shown the employment of SFE for removal of contaminants from
fish oil and fish tissue, respectively, using carbon dioxide. The contaminants were
polychlorinated biphenyls and pesticides.
The use of SFC for the separation of fish oil related compounds has until
recently focused on model mixtures, like saturated triglycerides (White and
354 A. Staby and J. MolleruplFluid Phase Equilibria 91(1993) 349-386

Houck, 1985) or a very limited number of fatty acids (Chester, 1984) or fatty acid
esters (Giirner and Perrut, 1989b)).Though, Huopalathi et al. (1988) published
the carbon number separation of triglycerides from rainbow trout using a non-
polar capillary column and carbon dioxide as the mobile fluid, and Staby et al.
(1993))have presented the separation of fatty acid ethyl esters derived from sand
launce utilizing both polar and non-polar capillary columns and carbon dioxide
as the elution fluid. Finally, Demirbtiker et al. (1992) have shown the application
of packed columns impregnated with silver nitrate to separate fish oil fatty acid
methyl esters using a composition gradient of the mobile phase consisting of
carbon dioxide, acetonitrile, and isopropanol.

APPLICATION OF THE DATA

If the object of the supercritical fluid separation is to produce the essential

fatty acids or triglycerides with a specific fatty acid composition, this can not be
accomplished by direct use of the natural occurring triglycerides from crude fish
oils due to their complex structure (Myher et al., 1990) and very low solubility.
Thus, most efforts are directed towards fractionating the free fatty acids or their
esters. Esters are much more soluble in supercritical fluids than the free fatty
acids and are thus preferentially treated. After separation of the individual esters,
specific triglycerides or free fatty acids can be reconstituted containing trace
amounts of the corresponding alcohol. Since ethanol is much less toxic than other
alcohols, ethyl esters are the obvious choice for processing of fatty acids from fish
oil for consumption.
Knowledge of the solubilities and phase equilibria of some individual key
components as well as of the natural mixtures in the supercritical fluid are of
great importance when designing for example a counter-current extraction
process. Thus, the kind of information provided by Figures 1 and 2 is indispens-
able for the choice of the optimal process conditions. Data on the solubilities and
phase equilibria must also used to develop reliable thermodynamic models for
prediction of various properties of multicomponent systems. For these purposes,
the phase equilibrium data are more usable and of greater importance than the
gas phase solubility data, especially for the binary systems, though more than half
of the information available are solubility data. In addition, of the data accessible
of the fatty acid ester systems, more than half concern the less important methyl
esters. Still, there is no doubt that a lot of unpublished material on the phase
equilibrium between fatty acid ethyl esters and supercritical fluids exists.
Most of the work published on the SFE of fish oil related compounds
concern batch extractions. Depart from the information about which components
can be extracted at certain conditions and the use of for instance analytical-scale
sample preparation SFE as an alternative to the Soxhlet extraction, these batch
A. Staby and J. Mollerup I Fluid Phase Equilibria 91 (1993) 349-386

CO2 Recycle

Reflux

Figure 3. Schematic diagram of a plant for continuous counter-current

supercritical fluid extraction and fractionation of fish oil fatty acid esters.

extractions of the major lipids are of little use in the design of continuous, large
scale separation processes because no equilibrium or steady state is reached.
Instead of these batch experiments, more work should be done on phase
equilibrium measurements and on continuous supercritical fluid fractionation
columns to estimate HETP values (height equal to a theoretical plate). Figure 3
shows a schematic diagram of a continuous supercritical fluid extraction and
fractionation plant, similar to the one presented by Krukonis et al. (1992). The
plant should be of the counter-current type with reflwr and be equipped with
both a stripping and an enriching section and a recycle of the supercritical fluid
(CO,). The ellipses represent the separators which may include a heat exchanger
and/or a pressure reducing valve. Pumps, pressure gauges, valves, etc. are not
shown in the Figure. The solvent could be carbon dioxide, either pure or with an
entrainer added to enhance the density of the solvent (ethanol should then be
preferred compared to methanol as mentioned above, though methanol has
better entrainer abilities), but adding an entrainer will cause a decrease in the
selectivity of the solvent. The feed material could be an ordinary ethyl esteri-
ficated fish oil or a urea fractionated fish oil. The urea fractionation might also
be done after the fractionation, but should anyway be performed in supercritical
carbon dioxide.
356 A. Staby and J. MolleruplFluid Phase Equilibria 91 (1993) 349-386

Even though the use of SFC for the separation of fish oil related compounds
has focused on model mixtures, SFC may have a future regarding at least two
application areas. The first concerns the further knowledge of the structure and
triglyceride composition of fish oil, both the size distribution of the fatty acids in
the triglycerides (Staby et al., 1993b)) and the appearance of the individual
triglycerides (Blomberg et al., 1993). The second application area is dedicated to
routine analysis of the various process steps in the refining of fish oils by
conventional methods as well as the on-line control of for instance the continuous
extraction and fractionation of a fish oil as shown in Figure 3.

LITERATURE RETRIEVAL INFORMATION

This review includes two Tables containing lists of references, the first
presenting experimental solubilities and phase equilibria of binary and multi-
component systems of supercritical fluids and fish oil related components, and
the second presenting separations of fish oil compounds using supercritical fluid
chromatography, extraction, and/or fractionation. The two Tables chronologically
listing the references are divided into five minor parts each according to the kind
of fish oil related compounds considered. The five parts are triglycerides, free
fatty acids, fatty acid methyl esters, fatty acid ethyl esters, and other components.
The references are found by a literature retrieval on Chemical Abstracts of
carbon dioxide and each single component as well as of fish and fish oils in
general. In addition, a manual search of the last 4 years of a number of journals
has been carried out, including: Fluid Phase Equilibria, Journal of the American Oil
Chemists Society, The Journal of Supercritical Fluids, Journal of Chemical and
Engineering Data, Journal of Chemical Engineering of Japan, Journal of the
American Instituteof Chemical Engineers, and Industrial and Engineering Chemistry
Research. The review includes papers published to the end of 1992 and a few
published in 1993.
The two Tables include the references, the experimental temperature and
pressure ranges, the number of data points/experiments, and some remarks to
the kind of compounds employed and data measured, but no evaluation or of the
data is given. Some relevant references may not be included, especially patents,
and papers written in Japanese, Chinese, or Russian may be difficult to trace.

SYSTEMS INVESTIGATED

The lists of references found are given in Tables 1 and 2. Table 1 presents the
experimental solubilities and phase equilibria of binary and multicomponent
A_ Staby and J. MolleruplFluid Phase Equilibria 91(1993) 349-386 357

systems of supercritical fluids and fish oil related components, and Table 2
presents the separations of fish oil compounds using supercritical fluid chroma-
tography, extraction, and/or fractionation. The meaning of the abbreviations in
the Remarks and components columns of the two Tables are given below.

frac.: fractionation of
ext.: extraction of
bi.: binary
ter.: ternary
mix.: mixture(s)
cont.: containing
prep.: preparative
cap.: capillary
chrom.: chromatographic
Sep.: separation of
Y: mass or mol fractions or solubilities of/in the vapor or supercritical
phase are given
X. mass or mol fractions or solubilities of/in the liquid phase are
given
g. 0.: data are given on graph(s) only and No. of data points are
estimated from the graph(s)
unav.: the information was unavailable to us
UCEP: the upper critical end point of the mixture is given
LCEP: the lower critical end point of the mixture is given
sol. enhanc.: data are given as solute solubility enhancement in the vapor or
supercritical phase
K: data are given as K-values
extract.: data are tentative given as the solute is extractable in the vapor or
supercritical phase at T, p
Xl, x2: mass or mol fractions of equilibrium liquid phases 1 and 2 are
given
mis.: the components are fully miscible
val.: value(s)
camp.: component(s)
+: and
K-val. data are given as partition coefficient value(s)
TA4BI.E 1 E
References of experimental measurements of sohtbilities/phase equilibria of fish oil related compounds in supercritical fluids. The references
are classified according to sohrbilities/phase equilibria of glycerides, free fatty acids, fatty acid methyl esters, fatty acid ethyl esters, and other
components.

Compound Reference Temperature Pressure No. of data Remarks and components

range (RI range (h4Pa) points

Glycerides
P
Peter et al. (1976) 323.2, 373.2 2 - 25 24 y, x, g. o., glyceride mix. of
mostly oleic acid and CO,
Stahl and Schilz (1976) 313.2 9.0 2 extract., di- or tristearin in CO,
Bnmner (1978) 323.2 - 398.2 2.5 - 25.7 72 y, x, oleic acid glyceride mix.
and CO, or qHd
Chrastil(1982) 313.2 - 353.2 8.1 - 25.3 66 y, pure t~bu~i~ t~p~t~
tristearin, triolein, or trilinolein
in CO,
King et al. (1983) 308.2 - 353.2 0.1 - 18.9 18 y, x, pure mono- or triolein and
CO2
Ohgaki et al. (1987) 298.2, 313.2 8.6 - 18.2 16 y, tripalmitin in CO,
Bamberger et al. (1988) 313 9.1 - 30.4 54 y, pure camp., bi., + ter. mix.
of trilaurin, trimyristin, + tri-
olein in CO,
Coorens et al, (1988) 298.4 - 431.8 0.3 * 13.1 244 y, x1, x2, XEP, UCEP, of tri-
palmitin and C,Hs
Brunetti et al. (1989) 313.2 - 333.2 20,30 (11) y, mean val. of pure camp. +
bi. mix, of triolein + tristearin
inC.0~
TABLE 1 (Continued)

Compound Reference Temperature Pressure No. of data Remarks and components

range (K) range (MPa) points

Imanishi et al. (1989) 313 - 353 20 - 35 342 K, triglycerides from sardine oil
and CO,
Peter and Ender (1989) 313.2 - 373.2 5.0 - 12.0 28 y, x, g. o., glyceride mix. of
mostly oleic acid and CO, or
C,H,
Consani and Smith (1990) 323.2 16.9 - 38.8 4 (y), mis. at T, p of glyceryl
monolaurate, dilaurate, or
monostearate with CO,
Gonqlves et al. (1991) 388.2 9.6 - 22.0 10 y, triolein in CO,
Nilsson et al. (1991) 323.2, 333.2 15.1 - 30.9 57 y, pure camp. + two ter. mix.
of mono-, di-, and triolein in
CO,
Bharath et al. (1992) 313.2 - 333.2 15.3 - 31.0 52 y, x, pure camp. + bi. mix. of
triolein + oleic acid and CO,
Hammam (1992) 388.2 - 333.2 8.0 - 35.0 48 y, g. o., tributyrin, tricaproin,
tricaprylin, tricaprin, trilaurin,
mono- and dilaurin in CO,
Bharath et al. (1993) 333.2, 353.2 5.3 - 31.8 39 y, x, pure tricaprylin, trilaurin,
or tripahnitin and CO,
Ashour and Hammam (1993) 308 - 338 15.0 - 40.0 31 y, pure mono-, di-, and trilaurin
in CO,
TABLE 1 (Continued)

Compound Reference Temperature Pressure No. of data Remarks and components

range (R) range (MPa) points

Fatty Acids

Francis (1954) 298.2 6.6 4 x1, x,, of pure lauric or oleic

acid and CO,
?
Czubryt et al. (1970) 313.2 30-200 26 g. o., sol. enhanc. of stearic acid S
in CO, 8
Peter et al. (1974) 375.2 15.3 2 y. x, of quaternary system of :
oleic acid, steak acid, GH,, E
and GH, %
Brunner (1978) 293.2 - 446.0 2.9 - 36.4 229 y, x, pure camp. + bi. mix. of &
steak and oleic acids and pure
$
camp. + bi. mix. of CO,, tY$,H, s
c;H,, CCIF,, + CBrF, z?
Peter and Brumrer (1978) 293.2 - 399.9 2.0 - 30.0 29 y, g. o., oleic acid in c;H,
Chrastil (1982) 313.2 - 333.2 8.1 - 25.3 25 y, pure steak, oleic, or behenic 2
8
acid in COl,
King et al. (1983) 8.5 - 19.1 1s y, oleic acid in CO, &
308.2,333.2 E.
Tiegs and Peter (1985) 313.2 - 373.2 10 - 60 27 y, g. o., pure camp. + bi. mix. 2
of steak and oleic acid in CO, o
Ohgaki et al. (1987) 298.2, 3 13.2 8.0 - 18.7 22 y, pahnitic acid in CO, s
Bamberger et al. (1988) 313 7.7 - 24.9 26 y, pure lauric, myristic, or pal- g
mitic acid in CO, S
Kramer and Thodos (1988) 318 - 338 14.2 - 57.5 19 y, palmitic acid in CO,
f
 +
TABLE 1 (Continued) %
k&
%
Compound Reference Temperature Pressure No. of data Remarks and components
:
range (K) range (MPa) points $
&
Peter et al. (1988) 313 - 353 5.0 - 20.0 74 y, x, g. o., pure CO, or GH, 2
with oleic acid G
Peter and Jakob (1988) 313.2 - 353.2 20 - 120 39 y, x, g. o., pure pelargonic or g
oleic acid and pure CO, or 3
C2H, B
Schmitt and Reid (1988) 310,320 11.4 - 36.4 18 y, stearic acid in CO, @
Ashour (1989) 313.2 10.0 - 30.0 20 y, pure oleic or palmitic acid in &
C.
CO2 9
Brunetti et al. (1989) 308.2 - 333.2 2430 (19) y, mean val. of bi. + ter. mix. E
myristic, palmitic, stearic, and ;:
oleic acid in CO, B
Imanishi et al. (1989) 313 - 353 20 48 y, x, differences of fatty acids g
from sardine oil in CO, in
vapor and liquid phases t
Kramer and Thodos (1989) 318 - 338 14.5 - 46.8 17 y, stearic acid in CO,
Consani and Smith (1990) 323.2 16.9 - 37.7 3 (y), mis. at T, p of capric, my-
ristic, or oleic acid with CO,
Zou et al. (19908)) 313.2, 333.2 6.3 - 28.8 48 y, x, pure oleic or linoleic acid
and CO,
Zou et al. (1990b)) 313.2, 333.2 5.8 - 28.7 78 y, x, of ter. system of oleic and
linoleic acid and CO,
Foster et al. (1991) 388.2, 318.2 9.6 - 20.1 12 y, oleic acid in CO,
Iwai et al. (1991) 380.2 8.1 - 23.0 12 y, pure myristic or palmitic acid
in CO, w
TABLE 1 (Continued)

Compound Reference Temperature Pressure No. of data Remarks and components

range (R) range (MPa) points

Nilsson et al. (1991) 323.2, 333.2 12.4 - 20.6 10 y, oleic acid in CO,
Bharath et al. (1992) 313.2 - 353.2 10.2 - 30.0 63 y, x, pure camp. + bi. mix. of
oleic acid + triolein and CO,
Maheshwari et al. (1992) 308 - 333 13.8 - 41.9 (63) y, pure lam-k, myristic, palmitic,
steak, oleic, or linoleic acid
and CO,
Yau et al. (1992) 373.2 - 473.2 1.01 - 5.07 90 y, x, pure lauric acid, palmitic
acid or arachidic acid and CO,
Yu et al. (1992) 313.2, 333.2 3.4 - 31.1 34 y, x, oleic acid and CO,
Bharath et al. (1993) 313.2 - 353.2 2.6 - 30.5 60 y, x, pure caproic acid, lauric
acid, or paImitic acid and CO,

Fatty Acid Methyl Esters

Hirohama (1986) 313.2 - 343.2 1.2 - 16.0 29 y, x, methyl myristate and CO,,
same as Inomata et al. (1989)
Wu et al. (1987) 313.2, 333.2 8.5 - 16.0 37 y, pure methyl myristate, stea-
rate, oleate, linoleate, or lau-
rate in CO,
Adams et al. (1988) 313.2, 343.2 4.1 - 20.0 17 y, x, methyl linoleate and CO,
Wu et al. (1988) 313.2, 333.2 8.5 - 16.0 38 y, g. 0. of same as Wu et al.
(1987) + bi. mix. of methyl
oleate + linoleate in CO,
TABLE 1 (Continued)

Compound Reference Temperature Pressure No. of data Remarks and components g

range (K) range (MPa) points

Cheng et al. (1989) 313.2, 343.2 2.0 - 19.7 78 y, x, pure CO, or G,H and g
methyl oleate S
Inomata et al. (1989) 313.2 - 343.2 1.0 - 20.4 215 y, x, pure methyl my&ate, E
palmitate, stearate, or oleate b
and CO,
f
Zou et al. (1989) 343.2 2.1 - 14.0 14 y, x, methyl linoleate + CO,
9
Zou et al. (19901)) 313.2, 333.2 3.8 - 20.3 52 y, x, pure methyl oleate or &
linoleate and CO, ;
Zou et al. (199ob)) 313.2, 333.2 4.7 - 21.0 48 y, x, ter. system of methyl ole-
ate and linoleate and CO, B
;:
Liong et al. (1991) 304.6 - 306.7 7.4 - 7.7 15 y, pure methyl DHA or EPA in 8
b
CO2
Nilsson et al. (1991) 323.2, 333.2 11.0 - 15.1 8 y, methyl oleate in CO,
Van Gaver (1992) 298 - 353 6.5 - 21.0 >200 y, x, various multi-camp. mix. f
methyl myristate, palmitate,
palmitolate, stearate, oleate,
linoleate, linolenate + pure
CO, or mix. CO, + GH, g. o.
Yu et al. (1992) 313.2, 333.2 2.9 -. 13.7 16 y, x, methyl oleate + CO,

Fatty Acid Ethyl Esters

Krukonis et al. (1987) 333.2 15.2 4 W-val. of fish oil esters and
CO,
TABLE 1 (Continued)

Compound Reference Temperature Pressure No. of data Remarks and components

range (R) range (MPa) points

Bharath et al. (1989) 313.2 - 333.2 1.1 - 21.1 329 y, x, pure ethyl stearate, oleate,
linoleate, EPA, or DHA and
CO2
Liang and Yeh (1991) 298.2 - 328.2 7 - 17 66 y, g. o., pure ethyl palmitate,
oleate, EPA, or DHA in CO,
Liong et al. (1991) 304.4 - 306.0 7.4 - 7.6 11 y, ethyl DHA in CO,
Liong et al. (1992) 313 - 373 9.0 - 25.0 46 y, g. o., pure ethyl oleate, eico-
satrienoate, arachidonate, or
DHA in CO,
Nilsson et al. (1992) 333.2 12.5 -40 K-val. of two menhaden oil
ester mix. and CO,
BorchJensen et al. (1993a)) 313.2, 343.2 5 - 20 unav. y, x, urea fractionated sand
launce oil mix. and CO,
Staby (1993) 283.2 - 343.2 2.0 - 21.5 86 y, x, sand launce oil mix. and
CO2
Staby et al. (1993) 283.2 - 343.2 2.0 - 21.5 86 y, x, sand launce oil mix. and
CO,, data also in Staby (1993)
Staby and Mollerup (1993) 283.2 - 343.2 2.0 - 21.5 86 y, x, sand launce oil mix. and
CO, data also in Staby (1993)

Other Components

Alwani (1980) 288 - 315 5 - 30 88 y, g. o, a-tocopherolacetat in Co, f

%
TABLE 1 (Continued)

Compound Reference Temperature Pressure No. of data Remarks and components

range (K) range (MPa) points

Chrastil (1982) 313.2 - 353.2 8.1 - 25.3 30 y, pure cholesterol or a-toco-

pherol in CO,
Wong and Johnston (1986) 308.2 - 333.2 10.1 - 27.9 21 y, cholesterol in CO,
Ohgaki et al. (1987) 298.2, 313.2 10.0 - 18.3 17 y, a-tocopherol in CO,
Ohgaki et al. (1988) 298,313 10 - 18 y, a-tocopherol in CO,, abstr.
Cygnarowin et al. (1990) 313 - 343 21.2 - 43.9 (32) y, g-carotene in CO,
Yeh et al. (1991) 298.2 - 328.2 6.9 - 17.2 12 y, cholesterol in CO,, g. O.
Yun et al. (1991) 313.2 - 333.2 10.0 - 25.0 17 y, cholesterol in CO,
Jay and Steytler (1992) 288.2 - 329.2 0 - 50 29 y, p-carotene in 12 different,
pure supercritical fluids
TABLE 2 E
References of experimental supercritical fluid extraction, fractionation and/or chromatography of fish oil related compounds. The references
are classified according to the separation of glycerides, free fatty acids, fatty acid methyl esters, fatty acid ethyl esters, and other components.

Compound Reference Temperature Pressure No. of Remarks and components

range (K) range (MPa) experiments

Glycerides

Passino (1949) (338.7 - 349.8) unav. (5) frac. menhaden oil, sardine oil, ?
and cod liver oil using C,H, S
Dickinson and Meyers (1952) (338.7 - 366.5) unav. frac. menhaden oil using C$Hs $
Zosel (1978) 300 - 363 101 - 162 (3 ext. and frac. fish liver oil using $,
C2H, S
Chester (1984) 363 19.3 - 23.7 1 cap. chrom. Sep. model mix. of e
glycerides using CO,
Krukonis (1984) unav. unav. unav. frac. anchovy oil using CO,, g
abstr. S
Fattori (1985) 328.2 36.0 (4) ext. pure camp. tripahnitin, f
triolein, and trieicosenoin and $
their ter. mix. using CO, $
Ikushima et al. (1985) 313, 333 9.8 - 27.0 11 ext. pure camp. tristearin and $
mix. with triolein using CO, E
White and Houck (1985) 363, 373 15.2 - 32.9 3 cap. chrom. Sep. model mix. of F
glycerides using CO, 2
Ikushima et al. (1986) 313 4.9 - 24.5 5 ext. mackerel powder using CO, ;:
Proot et al. (1986) 363 - 523 19.0 - 29.0 8 cap. chrom Sep. model mix. of g
sat. triglycerides using CO,
Suzuki et al. (1986) 313 15, 30 5 ext. raw fish using CO,
TABLE 2 (Continued)

Compound Reference Temperature Pressure No. of Remarks and components :

range (MPa) experiments %
range (K) z.

Yamaguchi et al. (1986) 313.2 - 353.2 25,40 7 ext. Antarctic krill oil using .!
3
co2
Elvevoll(1988) 309-328 8-28 6 ext. codfish viscera oil using k
(332
$
Hardardottir and Kinsella (1988) 313,323 13.8 - 34.5 28 ext. rainbow trout muscle using m
6
co2
E.
Huang (1988) 393 12 - 42 1 cap. chrom. Sep. fish oil using $
co2 ii.

Huopalahti et al. (1988) 423 13.8 - 37.9 1 cap. chrom. Sep. rainbow trout 2
oil using CO, 2
B
Ikushima et ai. (198gb)) 313,333 7.8 - 27.0 18 ext. tristearin and triolein using e
co2 iz

Berg and Greibrokk (1989) llnav. unav. 1 cap. chrom. Sep. marine oil E
using CO, %
Imanishi et al. (1989) 313 - 353 20 - 35 16 ext. of sardine oil using CO,
Nilsson et al. (1989b)) 333 13.8 - 43.1 4 ext. and frac. tri-EPA and tri-
DHA from synthetic mix. using
co2
Nomura (1989) 318 16.0 - 25.0 2 chrom. Sep. cod liver oil using
(332
Suprex Corporation (1989) 373,423 10.0 - 45.0 5 chrom Sep. salmon oil, cod liver
oil, and fish oil using CO,
Demirbtiker and Blomberg (1990) 348 28.3 - 32.4 1 chrom. Sep. fish oil using CO,

5
TABLE 2 (Continued)

Compound Reference Temperature Pressure No. of Remarks and components

range (K) range (MPa) experiments

Kallio and Laakso (1990) 423 24.1 - 34.4 (18) cap. chrom. Sep. model mix. sat.
triglycerides using CO,
Ring (1990) 393 15 - 36 1 cap. chrom. Sep. fish oil using
CO*
Taylor and Chang (1990) 393 12 - 35 2 chrom. Sep. fish oil using CO,
Kallio et al. (1991) 423 13.8 - 34.5 4 cap. chrom. Sep. Baltic herring
oil fractions using CO,
Adschiri et al. (1992) 313.2 - 373.2 10 (1) extractive reaction of tricapry-
lin, oleic acid + lipase in CO,
Blomberg et al. (1993) 373 34.0 2 chrom. Sep. fish oil using CO,
Borch-Jensen et al. ( 1993b)) 443 17.2 - 39.1 4 cap. chrom. Sep. sand launce oil
using CO,
Staby (1993) 433,443 20.3 - 39.7 8 cap. chrom. Sep. sand launce oil
using CO,
Staby et al. (1993b)) 323-443 14.9 - 39.1 7 cap. chrom. Sep. various fish
oils using CO,

Fatty Acids

Chester (1984) 363 13.2 - 19.3 1 cap. chrom. Sep. model mix. of
free fatty acids using CO,
Tiegs and Peter (1985) 333, 348 12.0 - 25.0 7 ext. mix. of stearic and oleic
acid using CO, and CrH, E
E
8
TABLE 2 (Continued)

Compound Reference Temperature Pressure No. of Remarks and components

range (R) range (MPa) experiments

Arai and Saito (1986) 313 15 2 frac. mix. cont. my&tic, palmit-
ic, stearic, oleic, linoleic, lino-
lenic, arachic, behenic, and
erucic acids using CO,
Bertucco et al. (1988) 333 11.7 - 23.3 3 ext. mix. cont. 80% oleic acid
using CO,
Imanishi et al. (1989) 313 - 353 20 - 35 16 ext. acids from sardine oil using
CO,
Daniels (1990) 308 - 368 9.3 - 9.7 unav. ext. + frac. herring oil using
CO,, abstr.
Kalinoski and Hargiss (1990) 398 10.0 - 40.0 1 cap. chrom. sep. hydrogenated
fish oil using CO,
Suzuki et al. (1990) unav. unav. unav. frac. polyunsaturated fatty acids
by urea adduct + CO,, abstr.
Adschiri et al. (1992) 313.2 - 373.2 10 (1) extractive reaction of oleic acid,
tricaprylin + lipase in CO,

Fatty Acid Methyl Esters

Krukonis (1984) unav. unav. unav. ext. fish oil esters using CO,,
abstr.
Arai and Saito (1986) 313 10 2 frac. sardine oil esters using
CO,
TABLE 2 (Continued)

Compound Reference Temperature Pressure No. of Remarks and components

range (K) range (MPa) experiments

Sm.&i et al. (1986) 323 12 2 ext. mix. of myristic and steak

esters using CO,
Ikushima et ai. (1988)) 313 8.8, 10.8 (2) ext. mix. of steak, oleic, linole-
ic, and Iinolenic esters using
P
CO, 3
Ikushima et al. ( 1988b)) 313 - 413 7.8 - 14.7 10 ext. two mix. of pahnitic, stea- g
ric, arachic, and behenic and of 2
steak, oleic, linoleic, and Iino-
1
lenic esters using CO,
EC
Kubota et al. (1988) unav. unav. unav. ext. fish oil esters using CO,, &
abstr. z
Giimer and Perrut (1989)) 311.8 - 328.2 15.4 - 30.7 4 chrom. Sep. model mix. of me- $
thy1 esters using CO, E
Giimer and Perrut (198gb)) 323.2, 323.7 18.7 - 19.2 3 chrom. sep. model mix. of pure k
methyl esters and with ethyl p
esters using CO, Fk
Ikushima et al. (1989) 305.313 9.3. 10.8 10 ext. mix. of stearic, oleic, linole- 2.
ic, and Iinolenic esters using z
w
CO, ii.
Kubota et al. (1989) unav. unav. unav. prep. chrom. Sep. fish oil esters z
using CO,, abstr. B
Higashidate et al. (1990) 313 8 - 20 1 ext. and prep. chrom. frac. E
sardine oil esters using CO, $
-
TABLE 2 (Continued)

Compound Reference Temperature Pressure No. of Remarks and components

range (R) range (MPa) experiments

Demirbtiker et ai. (1992) 348 - 388 28.4 - 36.5 5 chrom. Sep. fish oil and of
model mix. using CO,
Ikushima et ai. (1992) 323 7.8 - 18.6 21 ext. and frac. the pure camp.
stearic and linolenic esters and
a-tocopherol and their mix.
using co,
Van Gaver (1992) 313 - 358 5.0 - 14.5 34 ext. various multi-camp. mix.
methyl pahnitate, stearate,
oleate, linoleate, linolenate +
pure CO, or mix. CO, + GH,

Fatty Acid Ethyl Esters

Eisenbach (1984) 323 2.5 - 15.0 (2) ext. and frac. codfish oil esters
using CO,
Krukonis et al. (1987) 333 15.2 (1) frac. fish oil esters using CO,
Nilsson et al. (1988) 293 - 373 15.2, 17.2 34 frac. menhaden oil esters using
CO*
Giimer and Perrut (1989) 323.7 19.1 1 chrom. Sep. model mix. of ethyl
and methyl esters using CO,
Nilsson et al. (1989)) 313 - 373 11.0 - 15.2 9 frac. menhaden oil esters using
CO,
TABLE 2 (Continued)

Compound Reference Temperature Pressure No. of Remarks and components

range (R) range (MPa) experiments

Nilsson et al. (1989b)) 313 - 353 12.0 - 17.5 1 frac. EPA and DHA esters
from urea-fractionated menha-
den oil esters using CO, g.o.
Suzuki et al. (1989) unav. tmav. unav. ext. fish oil esters using CO,,
abstr.
Krukonis et al. (1992) 333 15.2 (1) frac. fish oil esters using CO,
Nilsson et al. (1992) 295 - 373 15.2 - 17.2 11 ext. and frac. menhaden oil
esters using CO,
Staby (1993) 333 - 413 7.2 - 29.9 9 cap. chrom. Sep. sand launce oil
using CO,
Staby et al. (1993)) 333 - 413 7.2 - 29.9 9 cap. chrom. sep. sand launce oil
using co,

Other Components

Giddings et al. (1968) 313.2, 413.2 20.3, 51.7 2 migration of cholesterol in

chromatographic column using
NH, or CO,
Stahl and Schilz (1976) 313.2 8.0, 8.5 2 ext. pure camp. squalene or
cholesterol by CO, at T, p
Matsumoto et al. (1986) 533 4.5 - 9.0 4 cap. chrom. sep. model mix. of
vitamins using CO,
Yamaguchi et al. (1986) 313 - 353 25 (24) ext. carotenoids from Antarctic
krill oil using CO,
 ?
TABLE 2 (Continued) I?
&
ii
Compound Reference Temperature Pressure No. of Remarks and components
range (K) range (MPa) experiments ;
F1

Bertucco et al. (1988) 333 11.7 - 23.3 3 ext. a-tocopherol from model :
mix. cont. 80% oleic acid using 2
6
CO,
Elvevoll (1988) 309-328 8 - 28 6 ext. ubiquinone, cholesterol, a-
9
tocopherol, retinol, squalene, &
and cholecalciferol from codfish 2
viscera oil using CO, 5
Hardardottir and Kinsella (1988) 313, 323 13.8 - 34.5 28 ext. cholesterol and phospho- $
lipids from rainbow trout mus- 2
cle using CO, ;:
B
Kubota et al. (1988) unav. unav. unav. ext. cholesterol from fish oil @
ester mix. using CO,, abstr.
Nam et al. (1988) 323 10.1 - 14.5 (60) ext. of polychlorinated com- E
pounds from fish tissue using 8
CO*
White et al. (1988) 413, 423 15.2 - 35.5 3 cap. chrom. sep. model mix. of
vitamins using CO,
Imanishi et al. (1989) 313 - 353 20 - 35 16 ext. cholesterol, sterol esters,
and phospholipids from sardine
oil using CO,
Krukonis (1989) 343 17.2 - 44.8 5 ext. of polychlorinated biphe-
nyls from codfish liver oil using
CO,
z
TABLE 2 (Continued)

Compound Reference Temperature Pressure No. of Remarks and components

range (K) range (MPa) experiments

Nam et al. (1989) 323 (14.2) (18) ext. of polychlorinated biphe-

nyls and pesticides from Mis-
souri River fish tissue using
CO2
Daniels (1990) 308 - 368 9.3 - 9.7 unav. ext. t frac. sterok, vitamins, +
pesticides using CO, abstr.
Nam et al. (1990) 323 13.9, 17.2 3 ext. of alkanes, aromatics, her-
bicides, and pesticides from fish
tissue using CO,
Jakobsson et al. (1991) 313 13.0 - 25.0 5 ext. dioxins and dibenzofurans
from cod liver oil using CO,
Nam et al. (1991) 323 17.2 4 on-line ext. and chrom. Sep. of
pesticides and polychlorinated
biphenyls from fish fillet tissue
using co,
Hammam (1992) 313 35.0 1 ext. dilauroyi phosphatidykho-
line using CO,
Ikushima et al. (1992) 323 7.8 - 18.6 18 ext. o-tocopherol, pure camp.
+ of synthetic mix. using CO,
Kapila et al. (1992) 323 17.2 4 on-line ext. and chrom. sep. of
pesticides and ~lychlorinated
biphenyls from fish fillet tissue
using CO,. Data same as Nam
et al. (1991)
Miles and Randall (1992) 343 11.1, 31.4 9 ext. pesticides from freeze-dried
fish tissue
A. Staby and J. MolleruplFluid Phase Equilibria 91(1993) 349-386 315

ACKNOWLEDGEh4ENTS

This work was supported by grants from Nordisk Industrifond and the Danish
Research Council.

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